Anthraquinone dyestuffs for cellulose-containing fibers

ABSTRACT

This invention relates to an anthraquinone dyestuff for cellulose containing fibers represented by the formula: ##STR1## wherein R 1  represents amino or hydroxyl, R 2  represents hydrogen, chlorine, bromine, cyano or --SO 2  R wherein R represents methyl, ethyl or phenyl, R 3  and R 4  each represents hydrogen, amino, hydroxyl, nitro, chlorine or bromine, Y represents a connecting group consisting of --O-- or --S--, one of X 1  and X 2  is hydrogen and the other is a group of the formula: ##STR2## wherein --Z-- represents a connecting group consisting of --O-- or --S--, --W 1  represents phenyl or --NR 6  R 7 , R 5  represents hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine or bromine, R 6  and R 7  each represents hydrogen or alkyl, alkenyl, cyclohexyl, aryl or aralkyl which may optionally be substituted by lower alkoxy, or NR 6  R 7  represents a 5-membered or 6-membered nitrogen-containing heterocyclic ring formed by combination of R 6  and R 7 , and n is 0 or 1, with the proviso that where X 2  is hydrogen, n is 0.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to anthraquinone dyestuffs forcellulose-containing fibers. More specifically, it relates toanthraquinone dyestuffs which dye cellulose-containing fibers,especially cellulose fibers and mixed fibers comprising polyester fibersand cellulose fibers, in bluish red to blue colors having excellentfastness properties.

2. Description of the Prior Art

A method for dyeing or print dyeing cellulose fibers or mixed fiberscontaining these fibers using a dyestuff of the following formula [II]and free from sulfonic acid or carboxylic acid groups: ##STR3## whereinR represents hydrogen or optionally substituted alkyl, aryl or acyl, Halrepresents chlorine or bromine, n represents a numeral of 1-2, and thering B may optionally be further substituted or may optionally becondensed, with the proviso that where R represents hydrogen or methyl,n must be >0 and/or B must further be substituted is known (JapanesePatent Application Laid-open No. 57078/1980), and the present inventorshave been intensively studying for further improvement, to discover thatthe dyestuffs of the formula [I] described herein can provide dyedproducts superior in wet fastness, wash fastness, etc. as compared withthe dyestuffs of the above formula [II], thereby having accomplishedthis invention.

SUMMARY OF THE INVENTION

An object of this invention is provide anthraquinone dyestuffs forcellulose-containing fibers which are of the formula [I]: ##STR4##wherein R¹ represents amino or hydroxyl, R² represents hydrogen,chlorine, bromine, cyano or --SO₂ R wherein R represents methyl, ethylor phenyl, R³ and R⁴ each represents hydrogen, amino, hydroxyl, nitro,chlorine or bromine, Y represents a connecting group consisting of --O--or --S--, one of X¹ and X² is hydrogen and the other is a group of theformula: ##STR5## wherein --Z-- represents a connecting group consistingof --O-- or --S--, --W¹ represents phenyl or --NR⁶ R⁷, R⁵ representshydrogen, methyl, ethyl, methoxy, ethoxy, chlorine or bromine, R⁶ and R⁷each represents hydrogen or alkyl, alkenyl, cyclohexyl, aryl or aralkylwhich may optionally be substituted by lower alkoxy, or NR⁶ R⁷represents a 5-membered or 6-membered nitrogen-containing heterocyclicring formed by combination of R⁶ and R⁷, and n is 0 or 1, with theproviso that where X² is hydrogen, n is 0.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The dyestuffs of the formula [I] above may be readily produced byreacting anthraquinone compounds of the formula [III]: ##STR6## whereinR¹, R², R³, R⁴, Y and n are as defined above, one of X³ and X⁴ ishydrogen, and the other is ##STR7## wherein R⁵ is as defined above, and--ZH represents hydroxyl or mercapto, with the proviso that where X⁴ ishydrogen, n is 0, with triazine compounds of the formula [IV]: ##STR8##wherein Hal represents active halogen, and W¹, R⁶ and R⁷ are as definedabove.

In the formulae [I] and [IV], examples of alkyl represented by R⁶ and R⁷include methyl, ethyl and straight-chain or branched-chain alkyl of 3-8carbon atoms, and examples of alkyl substituted by lower alkoxy include2-ethoxyethyl, 3-isopropoxypropyl, 3-(2-methoxyethoxy)propyl and2,2-diethoxyethyl.

Examples of alkenyl include allyl, 2-methylallyl, 3-methylallyl andstraight-chain or branched-chain alkenyl of 4-8 carbon atoms, andexamples of substituted alkenyl include 2-methoxyallyl and3-methoxyethoxyallyl.

Examples of aryl include phenyl, o-tolyl, p-ethylphenyl etc., andexamples of aryl substituted by lower alkoxy include p-methoxyphenyl,2,5-dimethoxyphenyl, m-ethoxyphenyl etc.

Examples of aralkyl include benzyl, phenethyl, m-methylbenzyl etc., andexamples of substituted aralkyl include p-methoxybenzyl, m-ethoxybenzyletc.

Examples of the nitrogen containing heterocyclic group represented byNR⁶ R⁷ include 1-pyrrolidinyl, 3-methyl-1-pyrrolidinyl,2-hydroxyethyl-1-pyrrolidinyl, 2,5-dimethyl-1-pyrrolidinyl,3-thiazolidinyl, 1-pyrrolyl, 1-pyrazolyl, 1-imidazolyl, morpholino,piperidino, 2,6-dimethylpiperidino, 1-piperadinyl,4-methyl-1-piperadinyl etc.

Amino of 3-10 carbon atoms in total is particularly preferred as NR⁶ R⁷.

For producing an anthraquinone dyestuff of the formula [I], ananthraquinone compound of the formula [III] and 1-1.2 molar times ofsaid anthraquinone compound of a monohalogenotriazine of the formula[IV] may be heated at 50°-130° C. in an organic solvent such as acetone,methyl ethyl ketone, toluene, nitrobenzene, dioxane,N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide etc. inthe presence of 1-2 molar times of said anthraquinone compound of anacid binding agent, for example, a tertiary amine such as triethylamine,tributylamine, N,N-diethylaniline etc. or an inorganic base such aspotassium carbonate, potassium bicarbonate etc. for about 0.5-5 hours.The resulting reaction mixture is cooled and then the formedprecipitates are separated by filtration, thereby an anthraquinonedyestuff of the formula [I] may be obtained.

Examples of the cellulose-containing fibers which are dyed with thedyestuffs according to this invention include natural fibers such ascotton, linen etc.; semi-synthetic fibers such as viscose rayon, copperammonia rayon etc., and modified cellulose fibers which are partiallyaminated or partially acylated. Of course, they may be woven or knittedfabrics or non-woven fabrics. Further, mixed yarns or mixed wovenfabrics of the above-described fibers and other fibers such as polyesterfibers, cation-dyeable polyester fibers, anion-dyeable polyester fibers,urethane fibers, di- or triacetate fibers etc. may also be dyed. Ofthose, the cellulose fibers and the mixed yarns or mixed woven fabricsof cellulose fibers and polyester fibers are particularly effectivelydyed with the dyestuffs of this invention.

As the method of dyeing the above-described cellulose-containing fiberswith the dyestuffs of this invention, a pad dyeing and print dyeing areparticularly preferred.

In dyeing, the dyestuff of the formula [I] above is preferably dispersedin a medium in a particle size of about 0.5 to 2μ. Examples of thedispersing method include a method which comprises finely dispersing thedyestuff in water by a grinder such as a sand grinder, a mill etc. usinga water-soluble dispersing agent such as a nonionic or anionicdispersing agent, e.g. sodium ligninsulfonate or a sodium salt of anaphthalenesulfonic acid--formaldehyde condensate, a method whichcomprises finely dispersing the dyestuff in a solvent other than water,for example, alcohols such as ethyl alcohol, isopropyl alcohol,polyethylene glycol etc., ketones such as acetone, methyl ethyl ketoneetc., hydrocarbons such as n-hexane, toluene, xylene, mineral terpeneetc., halogenated hydrocarbons such as tetrachloroethylene etc., esterssuch as ethyl acetate, butyl acetate etc., ethers such as dioxane,tetraethyleneglycol dimethyl ether etc., and mixed solvents thereof,using a dispersing agent sparingly soluble or insoluble in water such asa sulfosuccinic acid ester, or an addition product of nonylphenol etc.with a low mole of ethylene oxide etc., a method which comprises finelydispersing the dyestuff in a mixed system of water and a solvent freelycompatible with water chosen from the above-described solvents, etc.

Further, during the course of this dispersing, a polymer compoundsoluble in the respective dispersing media or a surface active agenthaving a main function other than the dispersing action may also beadded.

This fine dispersion of the dyestuff can be used as such as a paddingbath in pad dyeing or as a printing paste in print dyeing. In general,however, a diluted dispersion obtained by diluting the fine dispersionof the dyestuff to a concentration depending on the desired dyeingconcentration with water, a mixed system of a solvent freely compatiblewith water and water or an O/W or W/O emulsion in which the oily layeris a petroleum hydrocarbon such as mineral terpene etc. or a halogenatedhydrocarbon such as tetrachloroethylene etc. is employed as a paddingbath or as a printing paste.

In order to practice this invention advantageously in the preparation ofa padding bath or a printing paste, a cellulose fiber-swelling agent isadded. Further, for the purpose of preventing dry migration in paddyeing or for the purpose of controlling the viscosity of each colorpaste to an optimum value for various print dyeing methods, a thickener,for example, water-soluble polymer compounds such as sodium alginateetc. may also be added.

The cellulose fiber-swelling agent is not always required to be presentin the padding bath or in the printing color paste, and it mayalternatively be present in the fiber beforehand.

Any compound may be used as the cellulose fiber-swelling agent so longas it has a boiling point of 150° C. or higher and has an effect toswell cellulose fibers, and examples thereof include ureas such asN,N,N',N'-tetramethylurea etc., and polyhydric alcohols such aspolyethylene glycol, polypropylene glycol etc. or derivatives thereof.In particular, polyhydric alcohols having an average molecular weight ofabout 200-500 such as polyethylene glycol, polypropylene glycol etc. orderivatives thereof are preferred as the cellulose fiber-swelling agent.The amount of the cellulose fiber-swelling agent used is suitable about5-25% by weight, preferably about 8-15% by weight, based on the paddingbath or the printing color paste.

Dyeing of the above-described fibers with the dyestuffs of thisinvention may be conducted in the conventional manner, for example, byimpregnating or printing the thus prepared padding bath or printingcolor paste with or to cellulose fiber containing materials, drying thematerials, heat-treating the materials with hot air at 160°-220° C. orwith superheated steam for 30 seconds to 10 minutes, alternatively,treating the materials in a high pressure saturated steam at 120° to150° C. for 3 to 30 minutes, and then washing with hot water watercontaining a surface active agent.

By the process described above, dyed products which have been clearlyand uniformly dyed and have good light fastness and wet color fastnessmay be obtained.

This invention will be described below in more detail by reference tothe examples but is not deemed to be limited thereto so long as thisinvention is not beyond the gist thereof.

EXAMPLE 1

A dyestuff dispersion was prepared from a dyestuff compositionconsisting of 15 g of an anthraquinone dyestuff of the structuralformula: ##STR9## 15 g of a naphthalenesulfonic acid--formaldehydecondensate and 70 ml of water using a paint shaker as a finelydispersing machine.

Using this dyestuff dispersion, a printing color paste having thefollowing composition:

    ______________________________________                                        Dyestuff dispersion      6.5    g                                             5% Sodium alginate aqueous solution                                                                    55     g                                             Polyethylene glycol dimethyl ether                                                                     9      g                                             (average molecular weight: 400)                                               Water                  balance                                                Total                    100    g                                             ______________________________________                                    

was prepared. As polyester/cotton (mixing ratio: 65/35) mixed spun clothwas print dyed with the printing color paste using a screen print dyeingmachine, provisionally dried at 80° C. for 3 minutes, and then dryheated at 215° C. for 90 seconds to fix the paste. This was washed withwater, and then soaped with a detergent solution containing 2 g/l of anonionic surface active agent ("Scourol #900", trademark, manufacturedby Kao Soap Co., Ltd.) in a bath ratio of 1:30 for 20 minutes to obtaina blue dyed product having excellent wash fastness and light fastness.

The dyestuff used in this example was prepared as follows: 3.62 g of1,5-diamino-4,8-dihydroxy-2-(4'-hydroxyphenyl)-anthraquinone wasdissolved in 50 ml of N-methyl-2-pyrrolidone, 2.0 g of triethylamine,1.4 g of potassium carbonate and 2.8 g of2-chloro-4,6-di-n-butylaminotriazine were added thereto and stirred at100° C. for 3 hours to effect condensation. The resulting reactionmixture was added dropwise to 500 ml of water, the formed precipitateswere filtered out, washed with water, and dried to obtain 5.5 g of adark blue powder of the dyestuff of the above structural formula.

The λmax (acetone) of this dyestuff was 628 nm.

COMPARATIVE EXAMPLE 1

A blue dyed product was obtained by procedures similar to thosedescribed in Example 1 above but using a dyestuff described in Example 1of Japanese Patent Application Laid-open No. 57078/1980 and of thestructural formula: ##STR10## When the dyed products obtained in Example1 (Invention) and Comparative Example 1 (Comparison) were testedaccording to Japan Industrial Standard L 0860 (Dry Cleaning FastnessTest) and L 0844 Method A-4 (Wash Fastness Test), the dyed product dyedwith the dyestuff of this invention clearly exhibited superior fastness.

COMPARATIVE EXAMPLE 2

A blue dyed product was obtained by procedures similar to thosedescribed in Example 1 above but using a dyestuff described in Example 2of Japanese Patent Application Laid-open No. 57078/1980 and of thestructural formula: ##STR11## When the dyed products obtained in Example1 (Invention) and Comparative Example 2 (Comparison) were testedaccording to Japan Industrial Standard L 0860 (Dry Cleaning FastnessTest) and L 0844 Method A-4 (Wash Fastness Test), the dyed product dyedwith the dyestuff of this invention clearly exhibited superior fastness.

EXAMPLE 2

A dyestuff dispersion was prepared from a dyestuff compositionconsisting of 15 g of an anthraquinone dyestuff of the structuralformula: ##STR12## 15 g of a naphthalenesulfonic acid--formaldehydecondensate and 70 ml of water using a sand grinder as a finelydispersing machine.

Using this dyestuff dispersion, a printing color paste having thefollowing composition:

    ______________________________________                                        Dyestuff dispersion     7 g                                                   5% Sodium alginate aqueous solution                                                                  55 g                                                   Polypropylene glycol   12 g                                                   (average molecular weight: 300)                                               Water                  balance                                                Total                  100 g                                                  ______________________________________                                    

was prepared. A mercerized cotton broad (40 counts) was print dyed withthe printing color paste using a screen print dyeing machine, thenprovisionally dried at 80° C. for 3 minutes, and treated withsuperheated steam at 190° C. for 7 minutes.

Thereafter, washing treatment was performed according to the proceduresdescribed in Example 1 to obtain a blurish red dyed product havingexcellent light fastness and wet color fastness.

The dyestuff used in this example was produced according to theprocedures described in Example 1.

The λmax (acetone) of this dyestuff was 518 nm.

EXAMPLE 3

A dyestuff dispersion was prepared from a dyestuff compositionconsisting of 16 g of an anthraquinone dyestuff of the structuralformula: ##STR13## 10 g of polyoxyethylene glycol nonylphenol ether (HLB13.3) and 74 g of water by finely dispersing using a sand grinder.

Using this dyestuff dispersion, a padding bath having the followingcomposition:

    ______________________________________                                        Dyestuff dispersion     6 g                                                   Tetraethylene glycol dimethyl ether                                                                  15 g                                                   Water                  balance                                                Total                  100 g                                                  ______________________________________                                    

was prepared, a polyester/cotton (mixing ratio: 65/35) mixed spun clothwas impregnated therewith, then squeezed to a squeezing rate of 45%,dried at 100° C. for 2 minutes and dry heated at 200° C. for 1 minute tofix. This was then washed according to the procedures described inExample 1 to obtain a purple dyed product having excellent wet colorfastness. The dyestuff used in this example was produced according tothe procedures described in Example 1.

The λmax (acetone) of this dyestuff was 559 nm.

EXAMPLE 4

Print dyeing was conducted according to the procedures described inExample 1 by using anthraquinone dyestuffs set forth in the followingTables 1, 2, 3 and 4. The hue of each dyed product obtained and the λmax(acetone) of each anthraquinone dyestuff used are shown in Tables 1, 2,3 and 4.

                                      TABLE 1                                     __________________________________________________________________________    Structural Formula                                                             ##STR14##                             DyedHue of                                                                          (acetone)λ max            No.                                                                              R.sup.3                                                                          R.sup.4                                                                          Y   W           NR.sup.6 R.sup.7                                                                           Product                                                                             (nm)                              __________________________________________________________________________    1  H  H  O   NHC.sub.3 H.sub.6 OC.sub.3 H.sub.7 (i)                                                    NHC.sub.3 H.sub.6 OC.sub.3 H.sub.7 (i)                                                     Bluish red                                                                          518                                 2                                                                              "  "  "                                                                                  ##STR15##                                                                                 ##STR16##     "    "                                  3                                                                              "  "  "   NHC.sub.3 H.sub.7 (n)                                                                     N(CH.sub.2CHCH.sub.2).sub.2                                                                  "    "                                  4                                                                              "  "  "                                                                                  ##STR17##                                                                                 ##STR18##     "    "                                  5                                                                              "  "  "                                                                                  ##STR19##  N[C.sub.3 H.sub.7 (n)].sub.2                                                                 "    "                                  6                                                                              "  Br "                                                                                  ##STR20##  N[C.sub.4 H.sub.9 (n)].sub.2                                                               Rubine                                                                              530                                 7                                                                              "  H  S                                                                                  ##STR21##  NHC.sub.5 H.sub.11 (i)                                                                     Reddish purple                                                                      543                               __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    Structural Formula                                                             ##STR22##                                  DyedHue of                                                                           (acetone)λ max      No.                                                                              R.sup.2 Y   W              NR.sup.6 R.sup.7                                                                           Product                                                                              (nm)                        __________________________________________________________________________    1  Cl      O                                                                                  ##STR23##                                                                                    ##STR24##   Blue   611                           2                                                                              Br      "                                                                                  ##STR25##                                                                                    ##STR26##     "    612                         3  "       "                                                                                  ##STR27##                                                                                    ##STR28##     "    609                           4                                                                              CN      "                                                                                  ##STR29##     NHC.sub.6 H.sub.13 (n)                                                                     Greenish blue                                                                        634                           5                                                                              SO.sub.2 CH.sub.3                                                                     "                                                                                  ##STR30##     NH(CH.sub.2CHCH.sub.2)                                                                       "    622                           6                                                                              CONHC.sub.2 H.sub.5                                                                   S   N[C.sub.3 H.sub.7 (i)].sub.2                                                                 [C.sub.3 H.sub.7 (i)].sub.2                                                                  "    614                         __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    Structural Formula                                                             ##STR31##                      DyedHue of                                                                         (acetone)λ max                    No.                                                                              R.sup.5                                                                             W         NR.sup.6 R.sup.7                                                                          Product                                                                            (nm)                                      __________________________________________________________________________    1  H     NHC.sub.6 H.sub.13 (n)                                                                  NHC.sub.6 H.sub.13 (n)                                                                    Blue 630                                         2                                                                              "     NHC.sub.5 H.sub.11 (n)                                                                   ##STR32##   "    "                                          3                                                                              "                                                                                    ##STR33##                                                                               ##STR34##   "    "                                          4                                                                              OCH.sub.3                                                                            ##STR35##                                                                               ##STR36##   "   629                                         5                                                                              CH.sub.3                                                                             ##STR37##                                                                              NHC.sub.3 H.sub.7 (i)                                                                      "   633                                         6                                                                              Cl                                                                                   ##STR38##                                                                               ##STR39##   "   635                                       __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    Structural Formula                                                             ##STR40##                        DyedHue of                                                                         (acetone)λ max                  No.                                                                              R.sup.2                                                                          Y   W           NR.sup.6 R.sup.7                                                                         Product                                                                            (nm)                                    __________________________________________________________________________    1  H  O                                                                                  ##STR41##                                                                                 ##STR42## Reddish Purple                                                                     546                                       2                                                                              "  "                                                                                  ##STR43##                                                                                 ##STR44## Reddish  Purple                                                                     "                                        3                                                                              Cl "   NHC.sub.6 H.sub.13 (n)                                                                    NHC.sub.6 H.sub.13 (n)                                                                   Purple                                                                             554                                       4                                                                              "  "                                                                                  ##STR45##  NHC.sub.2 H.sub.5                                                                          "   "                                        5                                                                              "  "                                                                                  ##STR46##                                                                                 ##STR47##   "   "                                        6                                                                              Br "                                                                                  ##STR48##                                                                                 ##STR49##   "  553                                       7                                                                              H  S   NHC.sub.8 H.sub.17 (n)                                                                    NH.sub.2     "  551                                     __________________________________________________________________________

EXAMPLE 5

Pad dyeing was conducted according to the procedures described inExample 3 by using anthraquinone dyestuffs set forth in the followingTables 5, 6 and 7. The hue of each dyed product obtained and the λmax(acetone) of each anthraquinone dyestuff used are shown in Tables 5, 6and 7.

                                      TABLE 5                                     __________________________________________________________________________    Structural Formula                                                             ##STR50##                              DyedHue of                                                                          (acetone)λ max           No.                                                                              R.sup.3                                                                          R.sup.4                                                                          Y   W               NR.sup.6 R.sup.7                                                                        Product                                                                             (nm)                             __________________________________________________________________________    1  H  H  O   NHC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                            NHC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                      Bluish red                                                                          518                                2                                                                              "  "  "                                                                                  ##STR51##      NHC.sub.4 H.sub.9 (t)                                                                     "    "                                 3                                                                              "  "  "                                                                                  ##STR52##      NH.sub.2    "    "                                 4                                                                              "  "  "                                                                                  ##STR53##                                                                                     ##STR54##                                                                                "    "                                 5                                                                              "  "  S                                                                                  ##STR55##                                                                                     ##STR56##                                                                              Reddish purple                                                                      542                                6                                                                              "  "  O   N(C.sub.4 H.sub.9 (sec)).sub.2                                                                N(C.sub.4 H.sub.9 (sec)).sub.2                                                          Bluish red                                                                          518                                7                                                                              "  Cl "                                                                                  ##STR57##      NHC.sub.5 H.sub.11                                                                      Rubine                                                                              530                              __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________     ##STR58##                                ProductDyedHue                                                                     (nm)(acetone)λ          __________________________________________________________________________                                                  max                              1 H   H   O                                                                                  ##STR59##                                                                                  ##STR60##   Purple                                                                             559                                2                                                                             "   "   "                                                                                  ##STR61##                                                                                  ##STR62##   "    "                                  3                                                                             "   "   "                                                                                  ##STR63##                                                                                  ##STR64##   "    "                                  4                                                                             "   "   "                                                                                  ##STR65##                                                                                  ##STR66##   "    "                                  5                                                                             "   "   S   N(C.sub.2 H.sub.4 OC.sub.2 H.sub.5).sub.2                                                  N(C.sub.2 H.sub.4 OC.sub.2 H.sub.5).sub.2                                                  "    554                              6 NO.sub.2                                                                          OH  O   N(C.sub.4 H.sub.9 (n)).sub.2                                                               N(C.sub.4 H.sub.9 (n)).sub.2                                                               Blue 582                                7                                                                             "   "   "                                                                                  ##STR67##   NH.sub.2     "    "                                  8                                                                             "   "   "                                                                                  ##STR68##   NHC.sub.2 H.sub.5                                                                          "    "                                  9                                                                             "   "   S                                                                                  ##STR69##   NHC.sub.3 H.sub.7 (i)                                                                      "    584                               10                                                                             "   "   "                                                                                  ##STR70##                                                                                  ##STR71##   "    "                                 11                                                                             OH  NO.sub.2                                                                          O   NHC.sub.5 H.sub.11 (n)                                                                     NHC.sub.5 H.sub.11 (n)                                                                     "    586                             12 "   "   "   N(C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3).sub.2                                        N(C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3).                                sub.2        "    "                                 13                                                                             "   "   "                                                                                  ##STR72##                                                                                  ##STR73##   "    "                                 14                                                                             NH.sub.2                                                                          OH  "                                                                                  ##STR74##   NHC.sub.8 H.sub.17 (n)                                                                     "    610                               15                                                                             "   "   "                                                                                  ##STR75##                                                                                  ##STR76##   "    "                                 16                                                                             "   "   "                                                                                  ##STR77##   NHC.sub.5 H.sub.11 (n)                                                                     "    "                                 17                                                                             OH  NH.sub.2                                                                          "                                                                                  ##STR78##   NHC.sub.5 H.sub.11 (n)                                                                     "    612                               18                                                                             "   "   "                                                                                  ##STR79##   NHC.sub.4 H.sub.9 (n)                                                                      "    "                                 19                                                                             "   "   S   NHC.sub.3 H.sub.7 (i)                                                                      NHC.sub.3 H.sub.7 (i)                                                                      "    613                             __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________     ##STR80##                       ProductDyedHue of                                                                  (nm)(acetone)λ max               __________________________________________________________________________    1  CH.sub.3                                                                            ##STR81##  N(CH.sub.3).sub.2                                                                         Blue 629                                        2                                                                              "                                                                                   ##STR82##                                                                                 ##STR83##  "    "                                        3  OC.sub.2 H.sub.5                                                                   NHC.sub.8 H.sub.17 (n)                                                                    NHC.sub.8 H.sub.17 (n)                                                                    "    630                                      4  "    NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                              NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                              "    "                                        __________________________________________________________________________

What is claimed is:
 1. An anthraquinone dyestuff forcellulose-containing fibers which is of the formula: ##STR84## whereinR¹ represents amino or hydroxyl, R² represents hydrogen, chlorine,bromine, cyano or --SO₂ R wherein R represents methyl, ethyl or phenyl,R³ and R⁴ each represents hydrogen, amino, hydroxyl, nitro, chlorine orbromine, Y represents a connecting group consisting of --O-- or --S--,one of X¹ and X² is hydrogen and the other is a group of the formula:##STR85## wherein --Z-- represents a connecting group consisting of--O-- or --S--, --W¹ represents phenyl or --NR⁶ R⁷, R⁵ representshydrogen, methyl, ethyl, methoxy, ethoxy, chlorine or bromine, R⁶ and R⁷each represents hydrogen or alkyl, alkenyl, cyclohexyl, aryl or aralkylwhich may optionally be substituted by lower alkoxy, or NR⁶ R⁷represents a 5-membered or 6-membered nitrogen-containing heterocyclicring formed by combination of R⁶ and R⁷, and n is 0 or 1, with theproviso that where X² is hydrogen, n is
 0. 2. The anthraquinone dyestufffor cellulose-containing fibers according to claim 1 which is of theformula: ##STR86## wherein R⁸ represents hydrogen, chlorine or bromine,W² represents phenyl or NR⁹ R¹⁰, and R⁹ and R¹⁰ each represents hydrogenor alkyl or aryl which may optionally be substituted by lower alkoxy, orNR⁹ R¹⁰ represents a 5-membered or 6-membered nitrogen-containingheterocyclic ring formed by combination of R⁹ and R¹⁰.
 3. Theanthraquinone dyestuff for cellulose-containing fibers according toclaim 1 which is of the formula: ##STR87## wherein R¹¹ representschlorine, bromine, cyano, methylsulfonyl or ethylsulfonyl, W³ representsphenyl or NR¹² R¹³, and R¹² and R¹³ each represents hydrogen or alkyl oraryl which may optionally be substituted by lower alkoxy, or NR¹² R¹³represents a 5-membered or 6-membered nitrogen-containing heterocyclicring formed by combination of R¹² and R¹³.
 4. The anthraquinone dyestufffor cellulose-containing fibers according to claim 1 which is of theformula: ##STR88## wherein R¹⁴ and R¹⁵ each represents hydroxyl, aminoor nitro, W⁴ represents phenyl or NR¹⁶ R¹⁷, and R¹⁶ and R¹⁷ eachrepresents hydrogen or alkyl or aryl which may optionally be substitutedby lower alkoxy, or NR¹⁶ R¹⁷ represents a 5-membered or 6-memberednitrogen-containing heterocyclic ring formed by combination of R¹⁶ andR¹⁷.
 5. The anthraquinone dyestuff for cellulose-containing fibersaccording to claim 1 which is of the formula: ##STR89## wherein R¹⁸represents chlorine or bromine, W⁵ represents phenyl or NR¹⁹ R²⁰, andR¹⁹ and R²⁰ each represents hydrogen, or alkyl or aryl which mayoptionally be substituted by lower alkoxy, or NR¹⁹ R²⁰ represents a5-membered or 6-membered nitrogen-containing heterocyclic ring formed bycombination of R¹⁹ and R²⁰.
 6. The anthraquinone dyestuff forcellulose-containing fibers according to claim 1 which is of theformula: ##STR90## wherein W⁶ represents phenyl or NR²¹ R²², and R²¹ andR²² each represents hydrogen or alkyl or aryl which may optionally besubstituted by lower alkoxy, or NR²¹ R²² represents a 5-membered or6-membered nitrogen-containing heterocyclic ring formed by combinationof R²¹ and R²².
 7. The anthraquinone dyestuff for cellulose-containingfibers according to claim 1 which is of the formula: ##STR91##
 8. Theanthraquinone dyestuff for cellulose-containing fibers according toclaim 1 which is of the formula: ##STR92##
 9. The anthraquinone dyestufffor cellulose-containing fibers according to claim 1 which is of theformula: ##STR93##
 10. The anthraquinone dyestuff forcellulose-containing fibers according to claim 1 which is of theformula: ##STR94##
 11. The anthraquinone dyestuff forcellulose-containing fibers according to claim 1 which is of theformula: ##STR95##
 12. The anthraquinone dyestuff forcellulose-containing fibers according to claim 1 which is of theformula: ##STR96##